Copending application U.S. Ser. No. 10/072,241, filed concurrently herewith, entitled xe2x80x9cPhthalocyanine Compositions,xe2x80x9d with the named inventors Jeffery H. Banning, Nan-Xing Hu, James D. Mayo, James M. Duff, Roger E. Gaynor, Rosa M. Duque, and Nam S. Ro, the disclosure of which is totally incorporated herein by reference, discloses compounds of the formula 
wherein M is an atom or group of atoms capable of bonding to the central cavity of a phthalocyanine molecule, wherein axial ligands optionally can be attached to M.
Copending application U.S. Serial No. 10/072,210, filed concurrently herewith, entitled xe2x80x9cInk Compositions Containing Phthalocyanines,xe2x80x9d with the named inventors Donald R. Titterington, Michael B. Meinhardt, Jeffery H. Banning, James D. Mayo, James M. Duff, Roger E. Gaynor, and Harold R. Frame, the disclosure of which is totally incorporated herein by reference, discloses a phase change ink composition comprising a phase change ink carrier and a colorant compound of the formula 
wherein M is an atom or group of atoms capable of bonding to the central cavity of a phthalocyanine molecule, wherein axial ligands optionally can be attached to M. Also disclosed are printing processes using the phase change inks.
The present invention is directed to methods for preparing colorant compounds. More specifically, the present invention is directed to processes for preparing phthalocyanine colorant compounds particularly suitable for use in hot melt or phase change inks. One embodiment of the present invention is directed to a process for preparing a colorant of the formula 
wherein M is an atom or group of atoms capable of bonding to the central cavity of a phthalocyanine molecule, wherein axial ligands optionally can be attached to M, which comprises (a) reacting 3-n-pentadecylphenol with 4-nitrophthalonitrile in the presence of a base to form an alkylarylether adduct of phthalonitrile; and (b) reacting the alkylarylether adduct of phthalonitrile with either (i) a metal compound, or (ii) an ammonia-releasing compound in the presence of an alkanolamine solvent, or (iii) mixtures of (i) and (ii), to form the colorant.
In general, phase change inks (sometimes referred to as xe2x80x9chot melt inksxe2x80x9d) are in the solid phase at ambient temperature, but exist in the liquid phase at the elevated operating temperature of an ink jet printing device. At the jet operating temperature, droplets of liquid ink are ejected from the printing device and, when the ink droplets contact the surface of the recording substrate, either directly or via an intermediate heated transfer belt or drum, they quickly solidify to form a predetermined pattern of solidified ink drops. Phase change inks have also been used in other printing technologies, such as gravure printing, as disclosed in, for example, U.S. Pat. No. 5,496,879 and German Patent Publications DE 4205636AL and DE 4205713AL, the disclosures of each of which are totally incorporated herein by reference.
Phase change inks for color printing typically comprise a phase change ink carrier composition which is combined with a phase change ink compatible colorant. In a specific embodiment, a series of colored phase change inks can be formed by combining ink carrier compositions with compatible subtractive primary colorants. The subtractive primary colored phase change inks can comprise four component dyes, namely, cyan, magenta, yellow and black, although the inks are not limited to these four colors. These subtractive primary colored inks can be formed by using a single dye or a mixture of dyes. For example, magenta can be obtained by using a mixture of Solvent Red Dyes or a composite black can be obtained by mixing several dyes. U.S. Pat. Nos. 4,889,560, 4,889,761, and 5,372,852, the disclosures of each of which are totally incorporated herein by reference, teach that the subtractive primary colorants employed can comprise dyes from the classes of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, and Basic Dyes. The colorants can also include pigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, the disclosure of which is totally incorporated herein by reference. U.S. Pat. No. 5,621,022, the disclosure of which is totally incorporated herein by reference, discloses the use of a specific class of polymeric dyes in phase change ink compositions.
Phase change inks have also been used for applications such as postal marking and industrial marking and labelling.
Phase change inks are desirable for ink jet printers because they remain in a solid phase at room temperature during shipping, long term storage, and the like. In addition, the problems associated with nozzle clogging as a result of ink evaporation with liquid ink jet inks are largely eliminated, thereby improving the reliability of the ink jet printing. Further, in phase change ink jet printers wherein the ink droplets are applied directly onto the final recording substrate (for example, paper, transparency material, and the like), the droplets solidify immediately upon contact with the substrate, so that migration of ink along the printing medium is prevented and dot quality is improved.
Compositions suitable for use as phase change ink carrier compositions are known. Some representative examples of references disclosing such materials include U.S. Pat. Nos. 3,653,932, 4,390,369, 4,484,948, 4,684,956, 4,851,045, 4,889,560, 5,006,170, 5,151,120, 5,372,852, 5,496,879, European Patent Publication 0187352, European Patent Publication 0206286, German Patent Publication DE 4205636AL, German Patent Publication DE 4205713AL, and PCT Patent Application WO 94/04619, the disclosures of each of which are totally incorporated herein by reference. Suitable carrier materials can include paraffins, microcrystalline waxes, polyethylene waxes, ester waxes, fatty acids and other waxy materials, fatty amide containing materials, sulfonamide materials, resinous materials made from different natural sources (tall oil rosins and rosin esters, for example), and many synthetic resins, oligomers, polymers, and copolymers.
Colorants suitable for hot melt or phase change ink compositions include members of the phthalocyanine class of chromophore which have been appropriately modified by chemical substitution to make them soluble in the organic carrier composition. Many such phthalocyanine derivatives are known to have a good cyan color, and absorb light strongly in the wavelength region of from about 600 to about 700 nanometers. Further, their well-known high chemical, thermal, and photochemical stability make them particularly attractive for printing applications where archival print properties are desired. Most phthalocyanines soluble in organic media fall into three generic classes: axially-substituted phthalocyanines, tetra-peripherally-substituted phthalocyanines, and octa-peripherally-substituted phthalocyanines.
The first class is illustrated by the following structure: 
In the most well-known examples of this class, M is tetravalent silicon, germanium, or tin and L1 and L2 can each be either bulky alkylsiloxy groups, such as xe2x80x94OSiR3 (wherein R is, for example, n-hexyl) or long-chain oxyhydrocarbon groups. See, for example, xe2x80x9cSynthesis and photochemical properties of aluminum, gallium, silicon and tin naphthalocyanines,xe2x80x9d W. E. Ford, M. A. Rodgers, L. A. Schechtman, J. R. Sounik, B. D. Rihter, and M. E. Kenney, Inorg. Chem., 31 (1992), 3371;xe2x80x9cA silicon phthalocyanine and a silicon naphthalocyanine: synthesis, electrochemistry, and electrically-generated chemiluminescence,xe2x80x9d B. L. Wheeler, G. Nagasubramanian, A. J. Bard, L. A. Schechtman, and M. E. Kenney, J. Am. Chem. Soc., 106 (1984), 7404;the disclosures of each of which are totally incorporated herein by reference. Also reported are examples in which M=Si and L1 and L2 are dendritic groups; see, for example, xe2x80x9cHyperbranched macromolecules via a novel double-stage convergent growth approach,xe2x80x9d K. L. Wooley, C. J. Hawker, and J. M. J. Frechet, J. Am. Chem. Soc., 113 (1991), 4252, the disclosure of which is totally incorporated herein by reference. A special class of such molecules are those in which M is a divalent transition metal, such as iron, cobalt, zinc, or ruthenium, and L1 and L2 are neutral coordinating ligands, such as pyridine, quinoline, or 1,4-diazabicyclo[2,2,2]octane; see, for example, xe2x80x9cSynthesis and properties of conducting bridged macrocyclic metal complexes,xe2x80x9d M. A. Hanack, Molecular Crystals and Liquid Crystals, 105 (1984), 133;xe2x80x9cNew adducts of phthalocyanine cobalt(II) with pyridine and 4-methylpyridine and their vibrational, magnetic and electronic properties I. Reactivity towards oxygen,xe2x80x9d F. Cariati, D. Galizzioli, F. Morazzoni, and C. Busetto, J. Chem. Soc., Dalton Trans. (1975), 556, the disclosures of each of which are totally incorporated herein by reference.
Peripherally tetrasubstituted phthalocyanines soluble in organic media are also known. Substituents can be either at the 2- (or 3-) positions, or at the 1- (or 4-) positions, as illustrated below, and typically are bulky (e.g. tertiary-alkyl) or contain long alkyl chains (e.g., more than about five carbons): 
Some reported examples of R-groups conferring solubility are tert-butyl (xe2x80x9cPhthalocyanines and related compounds IX. Synthesis and electronic absorption spectra of tetra-t-butylphthalocyanines,xe2x80x9d S. A. Mikhalenko, S. V. Barknova, O. L. Lebedev, and E. A. Luk""yanets, Zhur. Obschei Khimii, 41 (1971), 2375, the disclosure of which is totally incorporated herein by reference), neopentyloxy (xe2x80x9cBinuclear phthalocyanines covalently linked through two-atom and four-atom bridges,xe2x80x9d S. M. Marcuccio, P. I. Svirskaya, S. Greenberg, A. B. P. Lever, C. C. Leznoff, and K. B. Tomer, Can. J. Chem., 63 (1985), 3957, the disclosure of which is totally incorporated herein by reference), 4-cumylphenoxy (xe2x80x9cMolecular association and monolayer formation of soluble phthalocyanine compounds,xe2x80x9d A. W. Snow and N. L. Jarvis, J. Am. Chem. Soc., 106 (1984), 4706, the disclosure of which is totally incorporated herein by reference), oligo(ethyleneoxy) (xe2x80x9cLyotropic and thermotropic mesophase formation of novel tetra[oligo(ethyleneoxy)]-substituted phthalocyanines,xe2x80x9d N. B. McKeown and J. Painter, J. Materials Chem., 4 (1994), 1153, the disclosure of which is totally incorporated herein by reference), long-chain alkysulfamoyl, RNHSO2xe2x80x94 (R. E Wyant, German Offenlegungsschrift, 2,224,063 (1973), the disclosure of which is totally incorporated herein by reference), long-chain alkyl carboxylate, ROCOxe2x80x94 (xe2x80x9cHighly ordered monolayer assemblies of phthalocyanine derivatives,xe2x80x9d K. Ogawa, S. Kinoshita, H. Yonehara, H. Nakahara, and F. Fukuda, J. Am. Chem. Soc. Chem. Comm., (1989), 477, the disclosure of which is totally incorporated herein by reference), and long-chain alkyl carboxamide, RNHCOxe2x80x94 (xe2x80x9cSelf-assembling features of soluble nickel phthalocyanines,xe2x80x9d M. Fujiki, H. Tabei, and T. Kurihara, J. Phys. Chem. 9 (1988), 1281, the disclosure of which is totally incorporated herein by reference).
A common feature of all such tetrasubstituted phthalocyanines is that they are obtained as a mixture of four constitutional isomers resulting from statistical cyclotetramerization of four isoindolenine units (xe2x80x9cSynthesis and Chromatographic separation of tetrasubstituted and Unsymmetrically substituted phthalocyanines,xe2x80x9d G. Schmid, M. Sommerauer, M. Geyer, and M. Hanack, in Phthalocyaninesxe2x80x94Properties and Applications, C. C. Leznoff and A. B. P. Lever, Editors, Volume 4, Chapter 1, the disclosure of which is totally incorporated herein by reference). These isomers, which are named according to their symmetry space group as C4h, D2h, C2v and Cs, are illustrated below: 
Statistical synthesis would give these four isomers in a ratio of 1:1:2:4, respectively. This phenomenon is described in more detail in xe2x80x9cSeparation of 2(3),9(10),16(17),23(24)-Tetrasubstituted Phthalocyanines with Newly Developed HPLC Phases,xe2x80x9d M. Sommerauer, C. Rager, and M. Hanack, J. Am. Chem. Soc., Vol. 118, No. 42, p. 10085 (1996), the disclosure of which is totally incorporated herein by reference, which discloses the synthesis of 2(3),9(10),16(17),23(24)-tetrasubstituted phthalocyanines from 1,2-dicyano-4-alkoxybenzenes or the corresponding isoindolines. In each case, four isomers with D2h, C4h, C2v, and Cs symmetry were obtained in the statistically expected yield. The separation of the C4h and the D2h isomers was achieved successfully for the first time from the other two isomers with newly developed HPLC phases based on xcfx80-xcfx80 interactions. In one case, a particular phthalocyanine could be separated into four different isomers and characterized by UV/VIS and 1H-NMR spectroscopy.
All four R groups in the class of tetrasubstituted phthalocyanines need not be identical. When two, differently-substituted, precursors are cyclotetramerized to form phthalocyanine, a mixture of six different isomers are possible (xe2x80x9cSynthesis and Chromatographic separation of tetrasubstituted and Unsymmetrically substituted phthalocyanines,xe2x80x9d G. Schmid, M. Sommerauer, M. Geyer, and M. Hanack, in Phthalocyaninesxe2x80x94Properties and Applications, C. C. Leznoff and A. B. P. Lever, Editors, Volume 4, Chapter 1, the disclosure of which is totally incorporated herein by reference). By using specially designed intermediates, it is possible to control the number of possible isomers. For example, xe2x80x9cSynthesis and Characterization of Di-disubstituted Phthalocyanines,xe2x80x9d J. G. Young and W. Onyebuagu, J. Org. Chem., Vol. 55, No. 7, p. 2155 (1990), the disclosure of which is totally incorporated herein by reference, discloses an improved approach to the synthesis of di-disubstituted phthalocyanines from two different phthalyl precursors wherein the resultant product contains two different R-groups. The method can be applied to the synthesis of hydrogen and metallo phthalocyanine. The yields are variable, ranging from 17 percent to 72 percent, depending on the substituents. Tetra-substituted phthalocyanines having different R groups are also described in xe2x80x9cSynthesis of Novel Unsymmetrical Substituted Push-Pull Phthalocyanines,xe2x80x9d A. Sastre, B. del Rey, and T. Torres, J. Org. Chem., Vol. 61, No. 24, p. 8591 (1996), the disclosure of which is totally incorporated herein by reference. This paper discloses the synthesis and characterization of novel, non-centrosymmetrically, push-pull substituted metal-free phthalocyanines. The compounds had different donor (dialkoxy, tert-butyl, methyl, p-tolylthio) and/or attractor (p-tolylsulfinyl, p-tolylsulfonyl, nitro) functional groups, were soluble in organic solvents, and were especially designed to study their second- and third-order nonlinear optical properties.
It is also possible, in certain cases, to obtain the 1(4) tetrasubstituted phthalocyanines as single isomers, as described in xe2x80x9cThe Synthesis of Pure 1,11,15,25-tetrasubstituted Phthalocyanines as Single Isomers Using Bisphthalonitriles,xe2x80x9d D. M. Drew and C. C. Leznoff, Synlett, 1994 (Ang), p. 623, the disclosure of which is totally incorporated herein by reference. This paper discloses bisphthalonitriles linked by 2,2-disubstituted propan-1,3-diol precursors which gave pure 1,11,15,25-substituted isomers of mononuclear phthalocyanine derivatives upon homocyclization. Reasonable yields of these phthalocyanines could be obtained with limited polymeric side-products utilizing modified cyclization methods. The 1H NMR spectrum of these phthalocyanines exhibited the discrete doublet-triplet-doublet proton signals expected of a pure isomer.
The third generic class of phthalocyanines soluble in common organic solvents is the peripherally octa-substituted compounds illustrated below. The substituents can occupy either the 1,4- or the 2,3-positions. These compounds are generally obtained as a single isomer. The solubility in a given solvent is related to the nature and chain length of the R group, with more than about five carbon atoms per chain being typical: 
Many examples have been reported for this class: 2,3-alkyl (xe2x80x9cAnnelides XXIX. Influence of the nature of the side-chains on the mesomorphic properties of octasubstituted phthalocyanine derivatives,xe2x80x9d K. Ohta, L. Jacquemin, C. Sirlin, L. Bosio, and J. Simon, New J. Chem., 12 (1988), 751, the disclosure of which is totally incorporated herein by reference), 1,4-alkyl (xe2x80x9cSynthesis and characterization of some 1,4,8,11,15,18,22,25-octaalkylphthalocyanines and 1,4,8,11,15,18,-hexaalkyl-22,25-bis(carboxypropyl)phthalocyanines,xe2x80x9d N. B. McKeown, I. Chambrier, and M. J. Cook, J. Chem. Soc. Perkin Trans., 1 (1990), 1169, the disclosure of which is totally incorporated herein by reference), 2,3-alkoxy (xe2x80x9cPreparation of ultrathin layers of molecularly controlled architecture from polymeric phthalocyanines by the Langmuir-Blodgett technique,xe2x80x9d E. Orthmann and G. Wegner, Angew. Chem. Int. Ed. Engl., 25 (1986), 1105, the disclosure of which is totally incorporated herein by reference), 1,4-alkoxy (xe2x80x9cSynthesis and characterization of some 1,4,8,11,15,18,22,25-octa(alkoxymethyl)phthalocyanines: a new series of discotic liquid crystals,xe2x80x9d A. N. Cammidge, M. J. Cook, K. J. Harrison, and N. B. McKeown, J. Chem. Soc. Perkin Trans., 1 (1991), 3053, the disclosure of which is totally incorporated herein by reference), 2,3-alkoxymethylene (xe2x80x9cA convenient synthesis of octasubstituted phthalocyanines,xe2x80x9d G. Pawlowski and M. Hanack, Synthesis (1980), 287; xe2x80x9cSynthesis of a polar discogen. A new type of discotic mesophase,xe2x80x9d C. Piechoki and J. Simon, Chem. Comm. (1985), 259, the disclosures of each of which are totally incorporated herein by reference), 1,4-alkoxymethylene (Octa-alkoxyphthalocyanine and naphthalocyanine derivatives: dyes with Q-band absorption in the far red or near infrared,xe2x80x9d M. J. Cook, A. J. Dunn, S. D. Howe, A. J. Thomson, and K. J. Harrison, J. Chem. Soc. Perkin Trans., 1 (1988), 2453, the disclosure of which is totally incorporated herein by reference), and 2,3-alkyldicarboximide (N. Kobayashi, Y. Nishiyama, T. Oya, and M. Sato, J. Chem. Soc. Chem. Comm., (1987), 390, the disclosure of which is totally incorporated herein by reference). Many of the compounds in this class exhibit liquid crystalline behavior as discussed in xe2x80x9cPhthalocyanine-Based Liquid Crystals: Towards Submicronic Devices,xe2x80x9d J. Simon and P. Bassoul, Chapter 6, Volume 4 of Phthalocyanines-properties and Applications, C. C. Leznoff and A. B. P. Lever (VCH Publishers Inc. N. Y.), the disclosure of which is totally incorporated herein by reference.
Substituted metal phthalocyanines may be prepared by, for example, the cyclotetramerization, generally in a high boiling solvent, of suitable precursors in the presence of a metal salt. Suitable precursors are substituted phthalonitriles, 1,3-diiminoisondolines, orthocyanobenzamide, phthalic anhydrides, and phthalimides. With the latter two precursors, a source of ammonia such as urea is provided to obtain phthalocyanine (F. H. Moser and A. L. Thomas, xe2x80x9cThe Phthalocyanines. Volume 1, Properties,xe2x80x9d CRC Press, 1983, the disclosure of which is totally incorporated herein by reference). Metal-free phthalocyanine can be obtained by, for example, refluxing phthalonitrile with ammonia gas in 2-N,N-dimethylaminoethanol (P. J. Brach, S. J. Grammatica, O. A. Ossanna, and I. Weinberger, J. Heterocyclic Chem., 7 (1970), 1403, the disclosure of which is totally incorporated herein by reference), by the condensation of phthalonitrile in hydroquinone solvent (J. A. Thompson, K. Murata, D. C. Miller, J. L. Stanton, W. E. Broderick, B. M. Hoffmann, and J. A Ibers, Inorganic Chem., 32 (1993), 3546, the disclosure of which is totally incorporated herein by reference), or by the treatment of dilithium phthalocyanine with acid (N. B. McKeown, I. Chambrier, and M. J. Cook, J. Chem. Soc. Perkin Trans., 1, (1990), 1169, the disclosure of which is totally incorporated herein by reference).
Some suitable precursors for synthesis of substituted phthalocyanines, such as 3- and 4-substituted phthalic anhydrides, phthalimides, and phthalonitriles, are commercially available (see, for example, Sigma-Aldrich Company""s Handbook of Fine Chemicals and Laboratory Equipment, the disclosure of which is totally incorporated herein by reference). Others can be prepared by, for example, oxidation of substituted ortho-xylenes (xe2x80x9cPhthalocyanines and related compounds IX. Synthesis and electronic absorption spectra of tetra-t-butylphthalocyanines,xe2x80x9d S. A. Mikhalenko, S. V. Barknova, O. L. Lebedev, and E. A. Luk""yanets, Zhur. Obschei Khimii, 41 (1971), 2375;xe2x80x9cKinetics and equilibrium in the ammonolysis of substituted phthalimides,xe2x80x9d R. A. McClelland, N. E. Seaman, J. M. Duff, and R. E. Branston, Can. J. Chem., 63 (1985), 121, the disclosures of each of which are totally incorporated herein by reference), treatment of substituted ortho-dibromobenzenes with copper cyanide (xe2x80x9cSynthesis of substituted o-phthalonitriles by the Rosemund von Braun reaction,xe2x80x9d E. I. Kovshev, L. I. Solov""eva, S. A. Mikhalenko, and E. A. Luk""yanets, Mendeleev Chemistry Journal, 21 (1976), 465, the disclosure of which is totally incorporated herein by reference) by reaction of the 4-nitrophthalonitrile with alkoxide or aryloxide ion (xe2x80x9cBinuclear phthalocyanines covalently linked through two-atom and four-atom bridges,xe2x80x9d S. M. Marcuccio, P. I. Svirskaya, S. Greenberg, A. B. P. Lever, C. C. Leznoff, and K. B. Tomer, Can J. Chem. 63 (1985), 3957; xe2x80x9cMolecular association and monolayer formation of soluble phthalocyanine compounds,xe2x80x9d A. W. Snow and N. L. Jarvis, J. Am. Chem. Soc. 106 (1984), 5706, the disclosures of each of which are totally incorporated herein by reference), or by the Diels-Alder reaction of substituted furans with fumaronitrile (xe2x80x9c1,4,8,11,15,18-hexaalkyl-22,25-bis(carboxypropyl)phthalocyanines: materials designed for deposition as Langmuir-Blodgett films,xe2x80x9d M. J. Cook, M. F. Daniel, K. J. Harrison, N. B. McKeown, and A. J. Thompson, J. Chem. Soc. Chem. Comm., (1987), 1148, the disclosure of which is totally incorporated herein by reference).
The above discussion is a brief summary of a large volume of published work related to soluble phthalocyanines. It is intended to be illustrative rather than comprehensive. Further information can be obtained from the following three textbooks: The Phthalocyanines, Volumes 1 and 2, by F. H. Moser and A. L. Thomas (CRC Press, 1983); Phthalocyaninesxe2x80x94Properties and Applications, Volumes 1 to 4, by C. C. Leznoff and A. B. P. Lever (VCH Publishers, Inc., 1993); Phthalocyanine Materials, by N. B. McKeown (Cambridge University Press, 1998); and references cited therein, the disclosures of each of which are totally incorporated herein by reference.
U.S. Pat. No. 5,847,114 (Thetford et al.), the disclosure of which is totally incorporated herein by reference, discloses the use of substituted phthalocyanines for the generation of singlet oxygen in which at least one of the peripheral carbon atoms in the 1-16 positions of the phthalocyanine nucleus (MxcexaPc) of Formula: 
wherein M is selected from H, metal, halometal, oxymetal, and hydroxymetal, and k is the inverse of 1/2 of the valency of M; is linked via an oxygen atom to an aromatic radical and the remaining peripheral carbon atoms are unsubstituted or substituted by any combination of atoms or groups and sulfonated derivatives thereof, provided that the phthalocyanine absorbs electromagnetic radiation at a wavelength from 650 nanometers to 800 nanometers.
U.S. Pat. No. 5,280,114 (Itoh et al.), the disclosure of which is totally incorporated herein by reference, discloses halogenated alkoxyphthalocyanine having a controlled grade of halogenation that can be prepared by reacting a single compound or a mixture of phthalocyanine represented by the formula: 
wherein R1 is a substituted or unsubstituted alkyl group and may be the same or different, and Met is two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal derivative, with 1 to 6 mole ratio of a halogenating agent at 0xc2x0 to 260xc2x0 C. in a solvent of from 1 to 1000 times by weight.
U.S. Pat. No. 5,149,800 (Kluger et al.), the disclosure of which is totally incorporated herein by reference, discloses a colorant for natural or synthetic resinous or polymeric materials, having the formula:
Axe2x80x94[Dxe2x80x94Zxe2x80x94SO2xe2x80x94N(R2)xe2x80x94Y]1-16
wherein R2 is selected from hydrogen, methyl, cyclohexyl, phenyl, or Y; A is a nonionic metallophthalocyanine chromophore which can be substituted for example with halogen, alkyl, alkoxy, alkylthio, or aryloxy; Z is an arylene moiety; D is a linking group being or containing at least one of xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94N(R3)xe2x80x94, or xe2x80x94N(SO2R4)xe2x80x94 as the linking moiety, wherein R4 is unsubstituted or substituted alkyl, cycloalkyl, or aryl, and R3 is R4 or hydrogen; Y is a poly(oxyalkylene) moiety containing at least three monomeric units of the formula (xe2x80x94ROxe2x80x94) wherein each R is straight or branched alkylene of 1-4 carbons or mixtures thereof, up to about 20 mole percent of said monomeric units may be connected by one or more linking groups such as alkyleneoxy, xe2x80x94NHxe2x80x94, or xe2x80x94NHCONHxe2x80x94, and wherein Y can be terminated by hydrogen, or by or contain as branch substituents, 1-3 groups or moieties selected from alkyl, cycloalkyl, acyl, or aryl; wherein any of the above recited hydrocarbon groups, moieties or substituents may themselves be substituted with up to four substituents selected, for example, from alkyl, halogen, mercapto, alkoxycarbonyl, hydroxy, alkoxy, or the like; and wherein each aliphatic hydrocarbon portion or moiety of the groups, moieties or substituents recited above contains from 1-20 carbons.
U.S. Pat. No. 4,875,903 (Pedrazzi), the disclosure of which is totally incorporated herein by reference, discloses compounds of the formula 
wherein each R1 is independently hydrogen, C1-4 alkyl, or C1-4 alkyl monosubstituted by hydroxy, halo, cyano, or C1-4 alkoxy, each of X1 and X3 is independently halo, hydroxy, C1-4 alkyl, C1-4 alkoxy, phenyl, phenoxy, amino, or an aliphatic, cycloaliphatic, aromatic, or heterocyclic amino group, each of X2 and X4 is independently an aliphatic, cycloaliphatic, aromatic, or heterocyclic amino group containing at least one protonatable nitrogen atom or quaternary ammonium group, m is 0 or 1, and each of n1 and n2 is independently 0 or 1, with the proviso that n1+n2 is 1 or 2, wherein each halo is independently fluoro, chloro, or bromo, with the provisos that (1) the total number of basic and cationic groups present as X1-X4 equals or exceeds the number of sulfo groups, (2) the hydroxy or alkoxy group of each hydroxy- or alkoxy-substituted alkyl group or alkylene radical attached to a nitrogen atom is bound to a carbon atom other than the C1-atom, and (3) the hydroxy groups of each alkylene radical substituted by two hydroxy groups are attached to different carbon atoms, mixtures of such compounds, and salts and mixtures with one or more copper phthalocyanine dyes containing basic and/or cationic groups. The materials are suitable for dyeing or printing hydroxy group- or nitrogen-containing organic substrates as such or in form of solid or liquid aqueous dye preparations. They are also suitable for dyeing glass and products thereof and the preparation of inks.
U.S. Pat. No. 3,674,494 (Hoffmann et al.), the disclosure of which is totally incorporated herein by reference, discloses improved relief plates, particularly printing plates, prepared by exposing under an image-bearing transparency a layer, which can be crosslinked by exposure and has been applied to a light-reflecting substrate of a substantially homogeneous mixture of solid polymers, monomers, photoinitiators, and, if desired, polymerization inhibitors, which mixture also contains finely dispersed therein a soluble metal complex dye, and washing out the unexposed areas.
PCT Patent Application WO 98/14520 (Wolleb), the disclosure of which is totally incorporated herein by reference, discloses a phthalocyanine or its metal complex of a divalent metal, oxometal, halogenometal, or hydroxymetal, which comprises at least one unsubstituted or substituted formyl, carbonyl, hydroxymethyl, or carboxyl group which is attached at the peripheral carbon skeleton. These phthalocyanines or their derivatives are used in recording layers of optical recording media. There is also claimed a novel process for the preparation of some of these compounds corresponding to the formula 
wherein M is a divalent metal, oxometal, halogenometal, or hydroxymetal, or two hydrogen atoms, X is halogen, or 2X in vicinal position on a phenyl ring form together a xe2x80x94Cxe2x95x90Cxe2x80x94Cxe2x95x90Cxe2x80x94 bridge so that an additional phenyl ring is obtained, Y is xe2x80x94OR1, xe2x80x94OOCR2, xe2x80x94NHR1, xe2x80x94N(R1)R2, or xe2x80x94SR1, x is 0 or a number from 1 to 8, y depending on z is a number from z to 4, and z is a number from 1 to 4, by reacting a compound of the formula 
wherein M, X, Y, x, and y are as defined above, with z moles each of dimethylformamide and phosphoryl chloride.
European Patent Application EP 0742255 (Wolleb et al.), the disclosure of which is totally incorporated herein by reference, discloses the coloration of high molecular weight organic materials in the mass with soluble phthalocyanine precursors of structure 
or isomers thereof, to the soluble phthalocyanine precursors as such wherein M is Zn, Ti, or V or wherein L1 is morpholino, pyrrolidino or C1-C12 alkyl substituted piperidino, to compositions containing high molecular weight organic materials and the above soluble phthalocyanine precursors, and to a process for making structured color images and applications thereof.
European Patent Application EP 787732 (Reynolds et al.), the disclosure of which is totally incorporated herein by reference, discloses phthalocyanine compounds substituted by from 1 to 8 substituents of formula (xe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94) wherein R is a 1,2-arylene group. Preferably, the phthalocyanine compounds are substituted by catechol. Additional substituents which may be present include hydrocarbyloxy, hydrocarbylthio, halogen, and sulfonic acid or a salt thereof.
European Patent Publication EP 1013721 (Stawitz), the disclosure of which is totally incorporated herein by reference, discloses solid preparations of metal-containing or metal-free phthalocyanine dyes which have an average particle size of greater than 100 microns and which have a pH of greater than or equal to 10 when dissolved in 10 times the amount of water. The dyes are particularly suitable for the dyeing and printing of paper, after dissolution in water.
European Patent Publication EP 540953 (Gerson et al.), the disclosure of which is totally incorporated herein by reference, discloses solid solutions containing (a) about 90 to about 10 percent by weight of a chlorinated copper phthalocyanine containing about 14 to about 16 atoms of chlorine per molecule, and (b) about 10 to about 90 percent by weight of a copper phthalocyanine containing about 3 to about 4 atoms of chlorine, wherein said compositions are characterized by X-ray diffraction patterns that differ from the sum of the X-ray diffraction patterns of the individual components.
European Patent Publication EP 714954 (Moeckli et al.), the disclosure of which is totally incorporated herein by reference, discloses cationic imidazole azo dyes of the formulae (1) (2) and (3) 
in which A and A1 independently of one another are each a radical of the formula (4) 
Z is the radical of an aliphatic or aromatic diamine, R1 and R2 are each hydrogen or substituted or unsubstituted C1-C4 alkyl or, together with the two nitrogen atoms to which they are attached and with Z, form a 5-, 6-or 7-membered ring, X is the radical of a bridging member, n is 2, 3 or 4, Z1 is the radical of an aromatic diamine, Z2 is the radical of an aliphatic diamine, KK is the radical of a coupling component, R3 and R4 are each hydrogen or substituted or unsubstituted C1-C4 alkyl, R5 and R6 independently of one another are each hydrogen or substituted or unsubstituted C1-C4 alkyl or C1-C4 alkoxy, and Anxe2x88x92 is a colorless anion, are particularly suitable for the dyeing of paper in red or violet shades having good fastness properties.
European Patent Publication EP398716 (Tsuchida et al.), the disclosure of which is totally incorporated herein by reference, discloses a pigment composition capable of giving a pigment dispersion which has excellent fluidity, high gloss, and high coloring power and is free from bluish tint, which comprises 100 parts by weight of at least one highly halogenated copper phthalocyanine and 0.3 to 30 parts by weight of a highly halogenated aluminum phthalocyanine.
European Patent Publication EP 209487 (Langley et al.), the disclosure of which is totally incorporated herein by reference, discloses pigmentary copper phthalocyanine prepared by converting crude copper phthalocyanine by methods known per se in the presence of trichlorophenoxy copper phthalocyanine. The resulting pigment is heat resistant and solvent resistant.
Japanese Patent Publication JP 8302224 (Toshihiro et al.), the disclosure of which is totally incorporated herein by reference, discloses a compound of formula I 
wherein R1 to R4 are each formula 11 
[R5 is an alkyl, an alkoxy, a (substituted) phenyl(oxy) or a benzyl(oxy)]; regarding the positions of R1 to R4, R1 is at C1 or C4, R2 is at C5 or C8, R3 is at C9 or C12, and R4 is at C13 or C16; M is a pair of H atoms, a divalent metal, or a metal derivative of a trivalent or tetravalent metal. Further, the compound is preferably obtained by reacting (A) a phthalonitrile compound of formula III 
with (B) a metal derivative (e.g. palladium chloride) e.g. in a ratio of the component B: the component A of 1:3 to 1:6 (mol ratio) in the presence of a catalyst such as 1,8-diazabicyclo[5,4,0]-7-undecene in a solvent such as n-aminoalcohol at 130-230xc2x0 C. for 5 to 15 hours. The compound has a high solubility and absorption coefficient and is capable of providing a color filter excellent in transparency behavior, light resistance, and heat resistance.
Japanese Patent Publication JP 8225751 (Masaji et al.), the disclosure of which is totally incorporated herein by reference, discloses a compound obtained by reacting (A) a phthalonitrile compound of formula I 
(COOR is a carboxylic acid ester having a heterocycle; X is a halogen, etc.; m is an integer of 0-3;n is an integer of 0-4) with (B) a metallic compound and expressed by (C) the formula II 
in which 1-8 pieces of benzene nuclei in 16 substitutable positions in a phthalocyanine skeleton are substituted with phenoxy and the phenoxy is substituted with a carboxylic acid ester having more than one heterocycles (M is a metal, a metal oxide or a metal halide). The objective optical recording medium is obtained by adding the compound to a recording medium placed on a substrate. The compound has excellent absorbing properties, solubility, light resistance, and economical efficiency and is useful for a near-infrared absorbing pigment, especially for an addition-type optical recording medium.
Japanese Patent Publication JP 9279050 (Shuichi et al.), the disclosure of which is totally incorporated herein by reference, discloses a phthalocyanine compound prepared by a process in which equimolar amounts of a phthalonitrile compound (e.g. 3-[4-t-butyl-xcex1-iso-propylbenzyloxy]phthalonitrile) represented by formula I 
and an organic base (e.g. 1,8-diazabicyclo[5.4.0]-7-undecene) are dissolved in a solvent (e.g. amyl alcohol) under heating. A metal compound (e.g. CuCl2 is added to the solution under agitation, and heated, and the solvent is removed from the reaction mixture in a vacuum after the reaction to obtain a phthalocyanine compound (e.g. compound represented by formula II) 
containing several isomers represented by formula III 
(wherein R1 to R4 are each a 1-6 C alkyl; R5 to R24 are each H, a halogen, a 1-6 C alkyl, a 1-6 C fluoroalkyl or the like; Z1, to Z4 are each H or a halogen; and M is a divalent metal atom, a tri- or tetra-valent substituted metal atom or the like). Next, a film of a mixture of the phthalocyanine compound with a binder is formed on a base made of, e.g. an acrylic resin by, e.g. spin coating to obtain a recording layer having a thickness of about 100 angstroms to 5 microns.
Japanese Patent Publication JP 5086301 (Naoto et al.), the disclosure of which is totally incorporated herein by reference, discloses compounds of formulas I to IV 
wherein R1 to R4 are each a 6 to 9 carbon alkyl group having 2 to 4 secondary, tertiary, or quaternary carbon atoms, Met is a divalent metal atom, a monosubstituted trivalent metal atom, or a disubstituted tetravalent metal atom, X is halogen, and n is 1 to 4. The compound is excellent in solubility in a solvent and useful as a compound for forming a recording layer of an optical recording medium which has high refractive index and sensitivity.
Japanese Patent Publication JP 5222302 (Koji et al.), the disclosure of which is totally incorporated herein by reference, discloses a phthalocyanine compound of the formula 
wherein X is F, OR2, or SR4, R1, R2, and R3 are each a 1 to 20 carbon alkyl group, a 4 to 6 carbon cycloalkyl group, or a phenyl, benzyl, or naphthyl group optionally substituted by halogen or by a 1 to 4 carbon alkyl or 1 to 4 carbon alkoxyl group, and M is a metal, a metal oxide, or a metal halide. The compound is produced by reacting a phthalonitrile compound of the formula 
with a metal oxide or halide or a metal salt of an organic acid of the formula MmXn wherein M is a metal or a metal oxide, X is O, halogen, or an organic acid group, and m and n are each 1 to 5. The phthalocyanine compound has an absorption band in the near-infrared region of 650 to 900 nanometers and an excellent solubility especially in an alcoholic solvent.
Japanese Patent Publication JP 62111249 (Norihito et al.), the disclosure of which is totally incorporated herein by reference, discloses a photosensitive composition principally comprising a photosensitive diazo resin and a lipophilic high molecular compound, wherein said photosensitive composition further contains a metal complex dye soluble in an organic solvent. Also disclosed is a photosensitive lithographic printing plate employing such a photosensitive composition.
Japanese Patent Publication JP 61146597 (Michitoku et al.), the disclosure of which is totally incorporated herein by reference, discloses a way to obtain a clear half-tone transfer picture of higher density levels than in the case of transfer using only dye by a method in which a thermal transfer ink sheet is made up using a filler and a dye so as to obtain the same hue and the recording density in the high-density region is complemented by the transfer of the filler. A toluene solution of polyester resin is coated on a base material of condenser paper and dried to form an intermediate adhesive layer. A solution of Kayaset blue-K-FL as a dye, an aliphatic amide as a low-melting substance, a paraffin wax as an auxiliary to lower the viscosity of the low-melting substance, and copper phthalocyanine as inorganic pigment filler in acetone is coated by a bar coater on the intermediate layer and dried to form an ink layer. A recording paper is laminated on the ink layer side of the ink sheet and solid transfer printing is made by using a thermal facsimile device to obtain clear cyanine-color transfer picture.
Japanese Patent Publication JP 58196295 (Makoto), the disclosure of which is totally incorporated herein by reference, discloses a way to recognize easily the surface part of a metal plate covered with a solid lubricant with the eye and to prevent the deterioration of pressing properties and dragging resistance caused by unevenness of coating, by adding a colorant to a solution of the solid lubricant. A solid lubricant consisting essentially of metallic soap, higher fatty acid, wax, etc. or a solid lubricant consisting essentially of an organic synthetic resin such as water-soluble acrylic polymer, etc. is blended with pigment or dye such as copper phthalocyanine blue, etc. in a volume ratio of usually (25:1)-(50:1).
Japanese Patent Publication JP 00290577 (Naoaki et al.), the disclosure of which is totally incorporated herein by reference, discloses a way to improve pigment-dispersing properties and resistance to drying by compounding a pigment, water, a water-soluble organic solvent and caprolactam. With a mixed solvent comprising water and 2 to 60 weight percent, preferably 5 to 35 weight percent, of a water-soluble organic solvent are admixed 1 to 25 weight percent, preferably 2 to 15 weight percent, of an inorganic pigment such as carbon black, ultramarine blue, or the like or an organic pigment such as copper phthalocyanine blue, benzidine yellow, or the like, 0.1 to 20 weight percent, preferably 1 to 10 weight percent of caprolactam of the formula and, as required, additives such as a pH adjusting agent, an antiseptic agent, a mildew-proofing agent, a fluorine-containing surfactant, a nonionic, anionic or cationic surfactant, an anti-foaming agent or the like. This ink composition hardly suffers from flocculation and sedimentation of pigments and can maintain not only the same density of handwriting as in the initial stage even when filled in a writing tool and left upright or upside-down but also the same volume of an ink discharged in writing as in the initial stage even when a writing tip is left exposed to the outside and the solid content is raised by evaporation of a solvent. xe2x80x9cSynthesis and Characterization of Di-disubstituted Phthalocyanines,xe2x80x9d J. G. Young and W. Onyebuagu, J. Org. Chem., Vol. 55, No. 7, p. 2155 (1990), the disclosure of which is totally incorporated herein by reference, discloses an improved approach to the synthesis of di-disubstituted phthalocyanines from two different phthalyl precursors. The method combines substituted 1,3-diiminoisoindoles and 6/7-nitro-1,3,3-trichloroisoindolenine to synthesize phthalocyanine. The method can be applied to the synthesis of hydrogen and metallo phthalocyanine. The yields are variable, ranging from 17 percent to 72 percent depending on the substituents. xe2x80x9cSeparation of 2(3),9(10),16(17),23(24)-Tetrasubstituted Phthalocyanines with Newly Developed HPLC Phases,xe2x80x9d M. Sommerauer, C. Rager, and M. Hanack, J. Am. Chem. Soc., Vol. 118, No. 42, p. 10085 (1996), the disclosure of which is totally incorporated herein by reference, discloses the synthesis of 2(3),9(10),16(17),23(24)-tetrasubstituted phthalocyanines from 1,2-dicyano-4-alkoxybenzenes or the corresponding isoindolines. In each case, four isomers with D2h, C4h, C2v, and Cs symmetry were obtained in the statistical expected yield. The separation of the C4h and the D2h isomers was achieved successfully for the first time from the other two isomers with newly developed HPLC phases based on xcfx80-xcfx80 interactions. In one case, a particular phthalocyanine could be separated into four different isomers and characterized by UV/vis and 1H-NMR spectroscopy. Because of line broadening at room temperature, T1 and T2 relaxation time measurements of two phthalocyanines at different temperatures were carried out. Whether the broad peaks are attributable to aggregation or attributable to a short relaxation time is explained.
xe2x80x9cThe Synthesis of Pure 1,11,15,25-tetrasubstituted Phthalocyanines as Single Isomers Using Bisphthalonitriles,xe2x80x9d D. M. Drew and C. C. Leznoff, Synlett, 1994 (Ang), p. 623, the disclosure of which is totally incorporated herein by reference, discloses bisphthalonitriles linked by 2,2-disubstituted propan-1,3-diol precursors which gave pure 1,11,15,25-substituted isomers of mononuclear phthalocyanine derivatives upon homocyclization. Reasonable yields of these phthalocyanines could be obtained with limited polymeric side-products utilizing modified cyclization methods. The 1H NMR spectrum of these phthalocyanines exhibited the discrete doublet-triplet-doublet proton signals expected of a pure isomer.
Phthalocyanines: Properties and Applications, C. C. Leznoff and A. B. P. Lever, eds., the disclosure of which is totally incorporated herein by reference, discloses at p. 35 various substituted phthalocyanines.
xe2x80x9cSynthesis of Novel Unsymmetrically Substituted Push-Pull Phthalocyanines,xe2x80x9d A. Sastre, B. del Rey, and T. Torres, J. Org. Chem., Vol. 61, No. 24, p. 8591 (1996), the disclosure of which is totally incorporated herein by reference, discloses the synthesis and characterization of novel non-centrosymmetrically push-pull substituted metal-free phthalocyanines. The compounds had different donor (dialkoxy, tert-butyl, methyl, p-tolylthio) and/or attractor (p-tolylsulfinyl, p-tolylsulfonyl, nitro) functional groups, were soluble in organic solvents, and were especially designed to study their second- and third-order nonlinear optical properties. For preparing the unsymmetrical phthalocyanines, the effectiveness of the subphthalocyanine route, using different substituted diiminoisoindolines as reagents, was tested. A comparison between this method versus the statistical one was done. The results obtained showed that the ring enlargement reaction of subphthalocyanines to obtain unsymmetrically substituted phthalocyanines is not a selective reaction but a multistep process, which depends dramatically on the nature of the substituents on the subphthalocyanines, the reactivity of the iminoisoindoline, the solvent, and other factors that limit its general synthetic utility. Preliminary data of the experimental second-order hyperpolarizabilities of some compounds were also given.
Although the phthalocyanines discussed above are considered to be soluble in organic media, they are not necessarily suited for use as phase change ink colorants. Accordingly, while known compositions and processes are suitable for their intended purposes, a need remains for improved colorant compositions. In addition, a need remains for improved phthalocyanine compositions. Further, a need remains for colorants suitable for use in phase change inks. Additionally, a need remains for colorants that enable good to excellent lightfastness. There is also a need for improved colorants having improved cyan color for primary subtractive imaging. In addition, there is a need for improved colorants having high tinctorial power or spectral strength. Further, there is a need for improved cyan phase change ink colorants that are highly thermally stable in ink compositions for several weeks in air at temperatures exceeding 140xc2x0 C. Additionally, there is a need for phase change ink colorants with low diffusion characteristic that will not bleed into inks containing other colorants. A need also remains for colorants with good to excellent lightfastness that are compatible with phase change ink vehicles. In addition, a need remains for colorants suitable for use in phase change inks that exhibit reduced or no variation in color over the life of the ink in the printer. Further, a need remains for colorants suitable for use in phase change inks that exhibit reduced or no variation in color subsequent to being deposited in imagewise fashion on substrates. Additionally, a need remains for colorants that have no carcinogenic or mutagenic effects. There is also a need for colorants that, when dissolved in phase change ink carriers, do not leave residues of material that might otherwise complicate filtration efficiency. There is also a need for phase change inks of good lightfastness that perform well when substrates imaged with the inks are passed through automatic document feed subsystems in copiers and printers. In addition, there is a need for phase change inks that exhibit reliable jetting characteristics and good long term performance in ink jet printers. Additionally, there is a need for preparative processes for phase change ink colorants that use low cost starting materials. A need also remains for preparative processes for colorants that use starting materials that are readily commercially available in large quantities. In addition, a need remains for preparative processes that use low cost, readily available solvents. Further, a need remains for preparative processes that do not generate hazardous waste that requires special handling and disposal procedures. Additionally, a need remains for methods for preparing colorants with the above advantages that enables preparation of a colorant product with reduced or no solubility problems in phase change ink vehicles as a result of incomplete reactions in the synthetic process. There is also a need for methods for preparing colorants with the above advantages that enables preparation of a colorant product without the need to handle unstable intermediate products with limited shelf life. In addition, there is a need for methods for preparing colorants with the above advantages that enables preparation of a colorant product without the need for severe reaction conditions. Further, there is a need for methods for preparing colorants with the above advantages that enables preparation of a colorant product without the need for elaborate purification procedures, such as column chromatrography or the like. Additionally, there is a need for methods for preparing colorants with the above advantages that enables preparation of a colorant product without the need to carry out dangerous derivatization procedures. A need also remains for methods for preparing colorants with the above advantages that enables preparation of a colorant product in high yield. In addition, a need remains for methods for preparing colorants with the above advantages that enables preparation of a colorant product in high purity. Further, a need remains for methods for preparing colorants with the above advantages that enables preparation of a colorant product with reduced costs associated with the synthesis. Additionally, a need remains for methods for preparing colorants with the above advantages that enables colorant synthesis with a high degree of reliability.
The present invention is directed to a process for preparing a colorant of the formula 
wherein M is an atom or group of atoms capable of bonding to the central cavity of a phthalocyanine molecule, wherein axial ligands optionally can be attached to M, which comprises (a) reacting 3-n-pentadecylphenol with 4-nitrophthalonitrile in the presence of a base to form an alkylarylether adduct of phthalonitrile; and (b) reacting the alkylarylether adduct of phthalonitrile with either (i) a metal compound, or (ii) an ammonia-releasing compound in the presence of an alkanolamine solvent, or (iii) mixtures of (i) and (ii), to form the colorant.
The present invention is directed to methods of making compounds of the formula 
wherein M is an atom or group of atoms capable of bonding to the central cavity of a phthalocyanine molecule, wherein axial ligands optionally can be attached to M. About seventy atoms or groups are known to bond in the central cavity of a phthalocyanine molecule, as disclosed in, for example, Phthalocyanine Materials, N. B. McKeown, Cambridge University Press (1998), Chapter 1, Table 1.1, the disclosure of which is totally incorporated herein by reference, including, but not limited to, two hydrogen, lithium, sodium, or potassium atoms; a divalent metal atom, such as beryllium, magnesium, calcium, strontium, barium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, lead, cadmium, and the like; a divalent halometal or -metalloid group, such as chloroiron(III), chlorotitanium(III), chlorochromium(III), chloroaluminum, chlorogallium, chloroindium, chlorophosphorus(III), dichlorotitanium(IV), dichlorosilicon, dichlorogermanium, dichlorotin, and the like, as well as the corresponding fluorides, bromides, and iodides; a divalent hydroxy metal group, such as hydroxyaluminum, hydroxygallium, dihydroxysilicon, dihydroxygermanium, dihydroxytin, and the like; a divalent oxo-metal group, such as oxo-molybdenum(IV), oxo-vanadium(IV), oxo-titanium(IV), and the like; a divalent metal- or metalloidal-oxyhydrocarbon group, such as alkoxyaluminum, alkoxygallium, dialkoxysilicon, diaryloxygermanium, and the like, wherein the oxyhydrocarbon group is an oxyalkyl group, an oxyaryl group, an oxyalkylaryl group, an oxyarylalkyl group, an oxyheterocyclic group, or mixtures thereof, and typically (although not necessarily) contains from one to about twenty carbon atoms; and the like, as well as mixtures thereof.
It is believed that in most instances the colorant molecules of the present invention are obtained as mixtures of four isomeric forms as illustrated below, wherein the C4h, D2h, C2v, and Cs, isomers are present in the approximate ratio of, respectively, about 1:1:2:4: 
In one embodiment, the colorant molecules of the present invention exhibit a spectral strength, measured as described prior to the Examples hereinbelow, in one embodiment of at least about 1xc3x97105 milliliters absorbance per gram, and in another embodiment of at least about 1.15xc3x97105 milliliters absorbance per gram, and in one embodiment of no more than about 1.5xc3x97105 milliliters absorbance per gram, and in another embodiment of no more than about 1.3xc3x97105 milliliters absorbance per gram, although the spectral strength can be outside of these ranges.
The colorant molecules of the present invention are prepared in two steps, the first of which is the synthesis of the alkylarylether adduct of phthalonitrile (4-(3-n-pentadecyl) phenoxyphthalonitrile): 
This process can be carried out by reacting the desired C15 phenol (3-n-pentadecylphenol) with 4-nitrophthalonitrile in the presence of a base. Examples of suitable C15 phenols are commercially available as, for example, CARDOLITE(copyright), predominantly a meta C15 alkyl phenol obtained from cashew nut distillation and containing small amounts of naturally occurring isomers thereof, available from Cardolite Corporation, Newark, N.J., and AF 6518, available from Palmer International Inc., Worchester Pa., also predominantly a meta C15 alkyl phenol obtained from cashew nut distillation and containing small amounts of naturally occurring isomers thereof. Suitable bases include both organic and inorganic bases. Examples of organic bases include (but are not limited to) trialkyl amines (including triethylamine, tripropylamine, tributylamine, and the like), piperidine, 1,4-diazabicyclo[2.2.2]octane, and the like, as well as mixtures thereof. Examples of inorganic bases include (but are not limited to) lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, lithium alkoxide, sodium alkoxide, potassium alkoxide (wherein the alkoxide can be, but is not limited to, methoxide, ethoxide, propoxide, butoxide (including t-butoxide), and the like), and the like, as well as mixtures thereof. The reactants are dissolved in any solvent capable of dissolving the reactants, such as methanol, ethanol, propanol, butanol, dioxane, acetone, toluene, nitrobenzene, dimethyl formamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone, 1-cyclohexyl-2-pyrrolidinone, sulfolane, and the like, as well as mixtures thereof. The solids content of the reaction mixture in one embodiment is at least about 0.5 parts by weight solvent per every 1 part by weight C15 phenol, and in another embodiment is at least about 2 parts by weight solvent per every 1 part by weight C15 phenol, and in one embodiment is no more than about 20 parts by weight solvent per every 1 part by weight C15 phenol, and in another embodiment is no more than about 6 parts by weight solvent per every 1 part by weight C15 phenol, although the solids content can be outside of these ranges. Typically, the C15 phenol and the base are added to the solvent, followed by heating the reaction mixture, in one embodiment to a temperature of at least about 30xc2x0 C., and in another embodiment to a temperature of at least about 80xc2x0 C., and in one embodiment to a temperature of no more than about 150xc2x0 C., and in another embodiment to a temperature of no more than about 120xc2x0 C., although the temperature can be outside of these ranges, for a period of time in one embodiment of at least about 0.25 hour, and in another embodiment of at least about 0.5 hour, and in one embodiment of no more than about 8 hours, and in another embodiment of no more than about 2 hours, although the time can be outside of these ranges. By allowing the C15 phenol and the base to react first, the C15 phenoxide salt is formed; optionally, the 4-nitrophthalonitrile can be added with the C15 phenol and the base in a single step, in which case the preheating step is eliminated. Thereafter, the 4-nitrophthalonitrile is added to the reaction mixture and the reaction mixture is then heated, in one embodiment to a temperature of at least about 30xc2x0 C., and in another embodiment to a temperature of at least about 70xc2x0 C., and in one embodiment to a temperature of no more than about 150xc2x0 C., and in another embodiment to a temperature of no more than about 110xc2x0 C., although the temperature can be outside of these ranges, for a period of time in one embodiment of at least about 0.25 hour, and in another embodiment of at least about 0.5 hour, and in one embodiment of no more than about 24 hours, and in another embodiment of no more than about 4 hours, although the time can be outside of these ranges. Thereafter, the reaction mixture is cooled, in one embodiment to a temperature of at least about 20xc2x0 C., and in one embodiment to a temperature of no more than about 100xc2x0 C., and in another embodiment to a temperature of no more than about 60xc2x0 C., although the temperature can be outside of these ranges, followed by quenching in a precipitant solvent, such as water, methanol, mixtures thereof, and the like, by stirring the reaction solution into the precipitant solvent or vice-versa, in an amount in one embodiment of at least about 0.25 part by weight precipitant solvent per every 1 part by weight reaction solution, and in another embodiment of at least about 0.5 part by weight precipitant solvent per every 1 part by weight reaction solution, and in one embodiment of no more than about 2 parts by weight precipitant solvent per every 1 part by weight reaction solution, and in another embodiment of no more than about 10 parts by weight precipitant solvent per every 1 part by weight reaction solution, although the relative amounts can be outside of these ranges, thereby causing precipitation of the alkylaryloxyphthalonitrile intermediate product, which can be isolated by filtration. Thereafter, the intermediate can be reslurried with water or dilute acid (for example, 2 percent wt/volume hydrochloric acid) or base (for example, 2 percent sodium hydroxide) and filtered, and then reslurried and filtered with pure water, and the process repeated until inorganic and/or organic salts are removed from the product and the filtrate is of neutral pH and has a conductivity of less than about 20 microSiemens. If desired, the product can be further purified by slurrying it in a solvent, such as methanol, ethanol, propanol, isopropanol, acetone, N,Nxe2x80x2-dimethylformamide, mixtures thereof, mixtures of one or more of these solvents with water, and the like, followed by isolation of the product by filtration, which process may remove minor organic contaminants from the alkylaryloxyphthalonitrile intermediate. Thereafter, the solid product can, if desired, be dried by heating under vacuum at a temperature in one embodiment of at least about 20xc2x0 C., and in another embodiment of at least about 25xc2x0 C., and in one embodiment of no more than about 100xc2x0 C., and in another embodiment of no more than about 50xc2x0 C., although the temperature can be outside of these ranges, for a period in one embodiment of at least about 1 hour, and in one embodiment of no more than about 72 hours, although the time can be outside of these ranges. The yield of the dried product typically (although not necessarily) ranges from about 80 to 90 percent. Purity of the final product in one embodiment (although not necessarily) is greater than about 98 percent, as ascertained by any conventional analytical technique, such as High Performance Liquid Chromatography (HPLC), Nuclear Magnetic Resonance (NMR) Spectroscopy, or Infrared (IR) Spectroscopy. Optionally, if desired, the product can be recrystallized by heating in a solvent, such as methanol, ethanol, isopropanol, and the like, cooling to about 0xc2x0 C., and filtering and drying the crystals.
For the synthesis of the alkylarylether adduct of phthalonitrile, the molar ratio of C15 phenol to 4-nitrophthalonitrile in one embodiment is at least about 1:1, and in one embodiment is no more than about 3:1, and in another embodiment is no more than about 1.5:1, although the molar ratio can be outside of these ranges, and the molar ratio of C15 phenol to base in one embodiment is at least about 1:1, and in one embodiment is no more than about 3:1, and in another embodiment is no more than about 1:1 to about 1.5:1, although the molar ratio can be outside of these ranges.
In this embodiment, the second step in the synthesis of the colorant molecules of the present invention entails conversion of the alkylarylether phthalonitrile adduct to the phthalocyanine: 
This process can be carried out by reacting the alkylarylether phthalonitrile adduct with a metal compound. Examples of suitable metal compounds include anhydrous and hydrated salts or complexes of the formula
MXn.yH2O
wherein M is a metal, such as lithium, sodium, potassium, beryllium, magnesium, calcium, scandium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, zinc, cadmium, aluminum, gallium, indium, silicon, germanium, tin, lead, and the like, X is an anion, such as a carboxylate-containing moiety, such as formate, acetate, acetoacetate, propionate, butyrate, benzoate, and the like, an alkoxide, such as methoxide, ethoxide, isopropoxide, or the like, acetyl acetonate, a halide atom, such as fluoride, chloride, bromide, or iodide, sulfate, alkyl sulfonate, aryl sulfonate, nitrate, nitrite, phosphate, and the like, n is a number representing the valence of the metal, and y is an integer of from 0 to 10. Specific examples include (but are not limited to) anhydrous copper chloride, hydrated copper chloride, anhydrous copper acetate, hydrated copper acetate, anhydrous copper sulfate, hydrated copper sulfate, anhydrous copper nitrate, hydrated copper nitrate, anhydrous copper bromide, hydrated copper bromide, and the like, as well as mixtures thereof. The alkylarylether phthalonitrile adduct, metal compound, and a solvent, such as ethylene glycol, amyl alcohol, hexanol, heptanol, tetralin, decalin, ISOPAR(copyright) (refined mineral spirits solvents available from Exxon), xylene, tributyl amine, N,N-dimethylaniline, quinoline, 1-chloronaphthalene, trialkanolamines, monoalkyl dialkanolamines, dialkyl monoalkanolamines (such as 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylamino-1-propanol, and the like), dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, sulfolane, and the like, as well as mixtures thereof, are combined to form the reaction mixture. The solids content of the reaction mixture in one embodiment is at least about 3 parts by weight alkylarylether phthalonitrile adduct per every 100 parts by weight solvent, and in another embodiment is at least about 10 parts by weight alkylarylether phthalonitrile adduct per every 100 parts by weight solvent, and in one embodiment is no more than about 60 parts by weight alkylarylether phthalonitrile adduct per every 100 parts by weight solvent, and in another embodiment is no more than about 30 parts by weight alkylarylether phthalonitrile adduct per every 100 parts by weight solvent, although the solids content can be outside of these ranges. The reaction mixture is heated to reflux. Reflux temperature in one embodiment is at least about 80xc2x0 C., and in another embodiment is at least about 140xc2x0 C., and in one embodiment is no more than about 250xc2x0 C., and in another embodiment is no more than about 190xc2x0 C., although the temperature can be outside of these ranges. The reaction mixture is refluxed for a period of time in one embodiment of at least about 1 hour, and in another embodiment of at least about 2 hours, and in one embodiment of no more than about 24 hours, and in another embodiment of no more than about 8 hours, although the time can be outside of these ranges. Thereafter, the reaction is cooled to a temperature in one embodiment of at least about 25xc2x0 C., and in another embodiment of at least about 50xc2x0 C., and in one embodiment of no more than about 150xc2x0 C., and in another embodiment of no more than about 100xc2x0 C., although the temperature can be outside of these ranges, filtered, typically through a filter of paper, glass fiber, polypropylene, GORETEX(copyright), and the like, although other methods of filtration can also be used, and washed with a solvent, such as water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, butanol, acetone, dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidinone, sulfolane, and the like, as well as mixtures thereof. If desired, the precipitated blue solids can then again be filtered, slurried with a solvent, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, butanol, acetone, dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidinone, sulfolane, and the like, as well as mixtures thereof, in relative amounts in one embodiment of at least about 3 parts by weight solvent per every 1 part by weight product, and in one embodiment of no more than about 100 parts by weight solvent per every 1 part by weight product, although the relative amounts can be outside of these ranges, for a period of time in one embodiment of at least about 0.5 hour, and in one embodiment of no more than about 24 hours, although the time can be outside of these ranges, and at a temperature in one embodiment of at least about 25xc2x0 C., and in another embodiment of at least about 50xc2x0 C., and in one embodiment of no more than about 200xc2x0 C., and in another embodiment of no more than about 100xc2x0 C., although the temperature can be outside of these ranges. The product is then filtered again and dried.
If desired, a catalyst or reaction promoter can also be included in the reaction mixture. Examples of suitable catalysts or reaction promoters include trialkanolamines, dialkyl monoalkanolamines, monoalkyl dialkanolamines, and the like, wherein the alkyl groups, which can be connected to the nitrogen atom through a primary, secondary, or tertiary carbon atom, in one embodiment have from 1 to about 6 carbon atoms, and in another embodiment have from 1 to about 3 carbon atoms, although the number of carbon atoms can be outside of these ranges, including (but not limited to) methyl, ethyl, n-propyl, isopropyl, and the like, and wherein the alkanol groups, which can be primary, secondary, or tertiary alkanols and can be connected to the nitrogen atom through a primary, secondary, or tertiary carbon atom, in one embodiment have from about 2 to about 6 carbon atoms, and in another embodiment have from about 2 to about 3 carbon atoms, although the number of carbon atoms can be outside of these ranges, including (but not limited to) 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and the like, with specific examples of suitable catalysts or reaction promoters including (but not limited to) 2-diethylaminoethanol, 2-dimethylaminoethanol, 2-dimethylamino-1-propanol, and the like, as well as mixtures thereof.
Suitable catalysts or reaction promoters also include ammonia-releasing compounds. Suitable ammonia-releasing compounds are any ammonium salts that release ammonia when heated, including (but not limited to) ammonium carbonate, ammonium carbamate, ammonium bicarbonate, ammonium molybdate, urea, ammonium salts of mono- and dicarboxylic acids, including (but not limited to) formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, oxalic acid, malonic acid, and the like, as well as mixtures thereof. When an ammonia releasing compound is employed as a catalyst or reaction promoter, while not required, in a specific embodiment, the reaction of the alkylarylether phthalonitrile adduct with the copper salt takes place with a two stage temperature-warming profile. The first stage entails heating the reaction mixture to an intermediate temperature, in one embodiment of at least about 80xc2x0 C., and in one embodiment of no more than about 140xc2x0 C., although the temperature can be outside of these ranges, and for a period of from time in one embodiment of at least about 0.25 hour, and in one embodiment of no more than about 3 hours, although the time can be outside of these ranges, during which time ammonia gas is slowly released. Thereafter, the reaction mixture is heated to a final temperature, in one embodiment of at least about 120xc2x0 C., and in another embodiment of at least about 140xc2x0 C., and in one embodiment of no more than about 250xc2x0 C., and in another embodiment of no more than about 190xc2x0 C., although the temperature can be outside of these ranges, and for a period of time in one embodiment of at least about 1 hour, and in another embodiment of at least about 2 hours, and in one embodiment of no more than about 24 hours, and in another embodiment of no more than about 10 hours, although the time can be outside of these ranges.
For the synthesis of the phthalocyanine compound, the molar ratio of 3-pentadecylphenoxy phthalonitrile adduct to metal compound in one embodiment is at least about 2:1, and in another embodiment is at least about 3:1, and in one embodiment is no more than about 10:1, and in another embodiment is no more than about 6:1, although the molar ratio can be outside of these ranges. When a catalyst or reaction promoter is used, the molar ratio of catalyst or reaction promoter to metal compound in one embodiment is at least about 0.1:1, and in another embodiment is at least about 0.5:1, and in one embodiment is no more than about 10:1, and in another embodiment is no more than about 2:1, although the molar ratio can be outside of these ranges.
In one embodiment of the present invention, two or more catalysts or reaction promoters can be used, such as one or more from the class of alkanolamines and one or more from the class of ammonia-releasing compounds, two or more from the class of alkanolamines, two or more from the class of ammonia-releasing compounds, or the like.
Metal-free phthalocyanine can be prepared by treatment of an alkali metal phthalocyanine such as dilithium, disodium, dipotassium, beryllium, magnesium, or calcium phthalocyanine, prepared according to the above process, with a dilute aqueous or alcoholic acid. Examples of suitable acids include (but are not limited to) hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, sulfonic acids, such as alkylsulfonic, arylsulfonic, arylalkylsulfonic, and alkylarylsulfonic, wherein the alkyl portions thereof can be linear or branched, in one embodiment with from 1 to about 18 carbon atoms, although the number of carbon atoms can be outside of this range, and wherein the aryl portions thereof in one embodiment have from 6 to about 12 carbon atoms, although the number of carbon atoms can be outside of this range, carboxylic acids, such as alkylcarboxylic, arylcarboxylic, arylalkylcarboxylic, and alkylarylcarboxylic, wherein the alkyl portions thereof can be linear or branched, and wherein the carboxylic acid in one embodiment has from 1 to about 24 carbon atoms, although the number of carbon atoms can be outside of this range (such as formic, acetic, propionic, benzoic, and the like), and the like, as well as mixtures thereof. The acid is present in the water or alcohol solution in any desired or effective concentration, in one embodiment of at least about 1 percent by weight acid, and in another embodiment of at least about 2 percent by weight acid, and in one embodiment of no more than about 10 percent by weight acid, and in another embodiment of no more than about 5 percent by weight acid, although the acid concentration can be outside of these ranges. Examples of suitable alcohols include (but are not limited to) methanol, ethanol, propanol, isopropanol, ethylene glycol, and the like, as well as mixtures thereof.
Alternatively, the metal-free phthalocyanine dye can be prepared by heating a concentrated solution of 4-(3-pentadecyl)phenoxyphthalonitrile in a dialkyl monoalkanola mine solvent, wherein the alkyl groups, which can be connected to the nitrogen atom through a primary, secondary, or tertiary carbon atom, in one embodiment have from 1 to about 6 carbon atoms, and in another embodiment have from 1 to about 3 carbon atoms, although the number of carbon atoms can be outside of these ranges, including (but not limited to) methyl, ethyl, n-propyl, isopropyl, and the like, and wherein the alkanol groups, which can be primary, secondary, or tertiary alkanols and can be connected to the nitrogen atom through a primary, secondary, or tertiary carbon atom, in one embodiment have from about 2 to about 6 carbon atoms, and in another embodiment have from about 2 to about 3 carbon atoms, although the number of carbon atoms can be outside of these ranges, including (but not limited to) 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and the like, with specific examples including 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylamino-1-propanol, and the like, as well as mixtures thereof, in the presence of an ammonia-releasing compound. The ratio by weight of 4-(3-pentadecyl)phenoxyphthalonitrile to dialkyl monoalkanolamine solvent in one embodiment is at least about 10:80, and in another embodiment is at least about 25:75, and in one embodiment is no more than about 60:40, and in another embodiment is no more than about 50:50, although the relative amounts can be outside of these ranges. Suitable ammonia-releasing compounds include those listed hereinabove with respect to catalysts or reaction promoters. The molar ratio of ammonia-releasing compound to 4-(3-pentadecyl)phenoxyphthalonitrile in one embodiment is at least about 0.1 molar equivalent ammonia-releasing compound per every 1 molar equivalent of 4-(3-pentadecyl)phenoxyphthalonitrile, and in another embodiment is at least about 0.5 molar equivalent ammonia-releasing compound per every 1 molar equivalent of 4-(3-pentadecyl)phenoxyphthalonitrile, and in one embodiment is no more than about 5 molar equivalents ammonia-releasing compound per every 1 molar equivalent of 4-(3-pentadecyl)phenoxyphthalonitrile, and in another embodiment is no more than about 2 molar equivalents ammonia-releasing compound per every 1 molar equivalent of 4-(3-pentadecyl)phenoxyphthalonitrile, although the relative amounts can be outside of these ranges. The mixture can be initially heated to a first temperature, in one embodiment of at least about 50xc2x0 C., and in another embodiment of at least about 65xc2x0 C., and in one embodiment of no more than about 130xc2x0 C., and in another embodiment of no more than about 125xc2x0 C., although the temperature can be outside of these ranges, for a period of time in one embodiment of at least about 10 minutes, and in another embodiment of at least about 20 minutes, and in one embodiment of no more than about 120 minutes, and in another embodiment of no more than about 60 minutes, although the time can be outside of these ranges, to promote slow release of ammonia, then is subsequently heated to a second temperature which is higher than the first temperature, in one embodiment of at least about 120xc2x0 C., and in another embodiment of at least about 135xc2x0 C., and in one embodiment of no more than about 200xc2x0 C., and in another embodiment of no more than about 170xc2x0 C., although the temperature can be outside of these ranges, for a period of time in one embodiment of at least about 1 hour, and in another embodiment of at least about 2 hours, and in one embodiment of no more than about 24 hours, and in another embodiment of no more than about 10 hours, although the time can be outside of these ranges. Thereafter, the reaction mixture is cooled, in one embodiment to a temperature of at least about 25xc2x0 C., and in another embodiment to a temperature of at least about 50xc2x0 C., and in one embodiment to a temperature of no more than about 125xc2x0 C., and in another embodiment to a temperature of no more than about 100xc2x0 C., although the temperature can be outside of these ranges, and the product is separated by filtration or by decantation and washed with a solvent, such as water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, butanol, acetone, dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidinone, sulfolane, and the like, as well as mixtures thereof. If desired, the precipitated blue solids can then again be filtered, slurried with a solvent, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, butanol, acetone, dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidinone, sulfolane, and the like, as well as mixtures thereof, in relative amounts in one embodiment of at least about 3 parts by weight solvent per every 1 part by weight product, and in one embodiment of no more than about 100 parts by weight solvent per every 1 part by weight product, although the relative amounts can be outside of these ranges, for a period of time in one embodiment of at least about 0.5 hour, and in one embodiment of no more than about 24 hours, although the time can be outside of these ranges, and at a temperature in one embodiment of at least about 25xc2x0 C., and in another embodiment of at least about 50xc2x0 C., and in one embodiment of no more than about 200xc2x0 C., and in another embodiment of no more than about 100xc2x0 C., although the temperature can be outside of these ranges. The product is then filtered again and dried.
If desired, the alkylarylether phthalonitrile adduct need not be isolated by addition of precipitant subsequent to its synthesis and prior to its reaction with the metal compound. In this embodiment, the reaction mixture in which the alkylarylether phthalonitrile adduct was formed can, if desired, optionally be filtered to remove any inorganic salts, followed by addition to the reaction mixture of the metal compound and, optionally, any desired reaction promoter. Thereafter, the reaction mixture is heated, to a temperature in one embodiment of at least about 120xc2x0 C., and in another embodiment of at least about 140xc2x0 C., and in one embodiment of no more than about 250xc2x0 C., and in another embodiment of no more than about 190xc2x0 C., although the temperature can be outside of these ranges, for a period of time in one embodiment of at least about 1 hour, and in another embodiment of at least about 2 hours, and in one embodiment for a period of time of no more than about 24 hours, and in another embodiment of no more than about 8 hours, although the time can be outside of these ranges. The phthalocyanine product thus formed can then be isolated as described hereinabove with respect to the two-step process.
Specific embodiments of the invention will now be described in detail. These examples are intended to be illustrative, and the invention is not limited to the materials, conditions, or process parameters set forth in these embodiments. All parts and percentages are by weight unless otherwise indicated. The purity of the synthesized dye products was determined using standard analytical procedures such as Nuclear Magnetic Resonance Spectroscopy (NMR) and High Performance Liquid Chromatography (HPLC). In addition, the purity of samples of the final phthalocyanine dyes was determined using a spectral strength (SS) measurement determined as follows: A mass of 50 milligramsxc2x12 milligrams of dye was weighed accurately to 0.1 milligram and transferred quantitatively to a 250 milliliter volumetric flask. Approximately 175 milliliters of spectroscopic grade toluene was then added to the flask to dissolve the dye thoroughly. The solution was diluted to the mark with toluene and mixed. Subsequently, 5.00 milliliters of dye solution was pipetted into a second 250 milliliter volumetric flask, which was diluted to the mark with toluene and mixed well. The UV/Visible absorption spectrum of the diluted dye solution was measured in the following way. An HP8452A UV/V is spectrometer or equivalent was used with standard 1 centimeter pathlength quartz cells. A baseline blank consisting of toluene was run. The absorbance of the dilute dye solution was determined at lambda max, which is the maximum absorption wavelength, typically 680 nanometers. The spectral strength was calculated by dividing the absorbance of the dilute dye solution at 680 nanometers by the concentration of the dilute dye solution in grams per milliliter. For the copper dyes, spectral strength values ranging from 1.1xc3x97105 to 1.3xc3x97105 A*ml/g were judged to be acceptable for phase change ink formulations. The highest value attained, 1.3xc3x97105 A*ml/g, is believed to be indicative of about 100 percent pure dye.